Lubricating composition



Patented Aug. 7, 1945,

LUBRICATIN G COMPOSITION "Lebbeus C. Kemp; 31- Scarsdale, N. Y.,assignor to The Texas Company, New York, N. Y., a corporation ofDelaware No Drawing. Application February 25, 1943,

, Serial No. 477,135

18 Claims. (01. 252-48) The presentinvention relates to lubricatingcompositions possessing extreme pressure properties, and particularly toan additive composition which, when incorporated in lubricating oils andgreases,- imparts extreme .pressure properties thereto.

The additive ingredients of the present inven-' tion are prepared-fromthe phenolic compositions present in or derived from the oils extractedfrom the nnacardium genus of the Anacardiaceae family. The oils includedwithin this classification are such oils as cashew nut shell oil,marking nut shell oil, Japanese lac, etc., whose chemical composition dpends upon the particular method of extraction used. It is'the consensusof the authorities on these extracted oils that the chemical compositionof the naturally-occurring oils "consists primarily of various types ofaromatic derivatives such as anacardic acid (C22Ha203),

cardol (C32H52O4), cardanol (CzoHazO), anacardol (Ciel-I300) urushiol(Gaol-13002), etc. These aromatic derivatives are very unstable and .inthe presence of heat form decomposition products or oil-insolublepolymerization products.

Representative of these naturally-occurring oils is cashew nut shelloilwhich, when obtained by solvent extraction, consists primarily of 90%The anacardic anacardic acid and cardol. acid portion of thissolvent-extracted oil, which is described as a salicylic acid homolog,decomposes at slightly elevated temperatures with-the evolu- Theseextreme pressure additives are prepared from the oil-soluble unsaturatedalkyl phenols present in or derived from the extracted oils and may takethe form of mono-di-or tri-esters of phosphoricacid, with preferencegivento the triester. Examples or the unsaturated alkyl phe-' nolssuitable for the preparation of these additives are cardanol, anacardol,urushiol, and the oil-soluble phenolic components which have not been,isolated and which may be present in admixture with other phenols in thedistillate and.

distillate residues of the extracted oils. These unsaturated alkylphenols are relatively unstable and susceptible to polymerization andcondensa-' tion reactions in the presence of acids and elevatedtemperatures. This instability may be overcome by partiallyhydrogenating the unsaturated constituents prior to the preparation ofthe substituted derivatives forming a part of the present invention, orby a choice of substitution reaction which will avoid polymerization.The stabilization of the unsaturated alkyl phenols is not critical tothe preparation of the phosphoric acid esters and as such is notintended as a lim- 'tion of carbon dioxide to yield .cardanol, which isa phenol containing an unsaturated alkyl radical (Gillian) in the metaposition. This decomposition is particularly noticed .in the cashew nutshell oil obtained by a thermal extraction process which contains onlyabout 16% anaoardic acid, I

with the balancemade up of a. major proportion of cardanoland a ,minorproportion of cardol.

It has been found than an ester of phosphoric acid in which the esterradical is derived from the unsaturated alkyl phenolsobtained from anoil extracted from the Anacardium genus of the Anacardiaceae familywhich have'been modified by the presence of one or more substituentgroups in 0 Motor oils Aircraft engine oils s I the unsaturated alkylradicals, is possessed of ex- I itation to the products of the presentinvention.

The phosphoric acid esters may be incorporated in a'hydrocarbon oil, andparticularly in mineral lubricating oils and greases in amounts ranging.between 0.l-10.0% weight, depending upon the type of hydrocarbon oilbase and the degree of extreme pressure properties desired. The particular range of proportions as applied to some of the lubricating oils andgrease bases may be outlined as follows:

Per cent by weight of y L finished lubricant Gear lubricants 0.5 5.0

Gear oils a 0.5 5.0.

Cutting oils 0.5 3.0 0.25- 1.5

0.5 2.0 Diesel oils 0.5 2.0

Turbine oils 0.1 0.5

In the preparation of the substituted unsaturated alkyl phenols and thephosphoric acid esters thereof, any of the classical methods ofsynthesis ceptional extreme pressure properties when incorporated in-a'hydrocarbon oil. These ester radicals are preferably those obtained fromthe aforementioned unsaturated alkyl phenols which contain either sulfuror a halogen such as chlorine or mixtures thereof in the unsaturatedalkyl radicals. Inaccordance with the present invention a high pressurelubricant is obtained by the addition of small quantities of thesephosphoricacid esters to a suitable lubricating oil or grease base. Asexamples oi these high pressure lubricants may be mentioned gearlubricants, gear oils, cutting oils, pressure greases, lubricating oilsfor internal combustion engines, etc. I

may be used. The particular methodschosen depend'upon the conditions ofreaction and the stability of. the phenolic compositions. When preparingthe sulfur and/or halogenated derivatlves of the unsaturated alkylphenols it is preferableto select a method of preparation which i iscarried out at low temperatures and which does not yield acidicby-products or where the acidic by-products are removed from thereaction zone. These conditions of reaction, however, may be' modifiedif the starting material has been stabilized by partial hydrogenation.

I The phosphoric acid esters of the substituted derivatives may beprepared by any of the generallyaccepted methods of preparation sincethe product resulting from the substitution reactions is suflicientlystable in and of itself to be-reacted under'normal conditions.

When preparing the halogenated derivatives and particularly achlorinated derivative, of the unsaturated alkyl phenols, the phenoliccompos n is p a y subjected to partial hydrogenchloride may be used inplace of the chlorine or hydrogen chloride previously mentioned.

' In preparing the sulfurized or sulfur-containing derivatives thephenolic composition may either be partially hydrogenated or reacted inits full unsaturated condition, depending upon the methods ofincorporating surfur.

The following example of the preparation of a tri-esi'er of phosphoricacid, in which the esterv radical was derived from partiallyhydrogenated sulfurized cardanol obtained from vcashew nutshell oil. isgiven as an illustration of one of the methods of preparing thesephosphoric acid esters:

, Example 400 cos. (370-380 grams) of freshly distilled cardanol with abromine no. of 118 was charged to an Adkins type bomb, together with10-15 grams of- Raney nickel. Hydrogen was admitted to 2000-2200 poundsper square inch and the results obtained (indicated uni pounds ofpressure required for seizure) were as follows:

Reference nil 5-10 Reference oi1+1.0% partially hydrogenated sulfurizedtri-cardanyl phosphate, 34.7

( Represents average of 6 test runs) Obviously many modifications andvariations of the invention as hereinbefore set'forth may be madewithout departing from the spirit and scope thereof, and therefore onlysuch limitations should be imposed as are indicated in theappendedclaims.

I claim: a 1. A lubrica'nt comprising a hydrocarbon oil containing0.1-l0.0% b'yweightof a substituted alkyl phenyl ester of phosphoricacid, said substituted alkyl phenyl ester being derived from theunsaturated alkyl phenols present in or derived from the oils extractedfrom the Anacardium' genus of the Anacardiaceae family and characterizedby the presence of at least one substituent group selected from theclassiconsisting of sulfur and halogen in the unsaturated alkyl radicalsthereof.

2. A lubricant comprising a mineral lubricating oil containing 0.1-10.0%by weight of a .substituted allryl phenyl ester of phosphoric acid, saidsubstituted alkyl phenyl ester being derived from the unsaturated alkylphenols present in 'or derivedfrom oils extracted from the Anacardiumbomb rocked at 250-300 1'. until the pressure dropped to 1000-1100pounds per square inch.

The process was repeated until a quantity of hy-- drogen had been addedsufncient to give a calculated bromine np. of 85-05. In this particularcase the resulting bromine no. was 95; After hydrogenation'the productwas illteredfree of Raneyrnickel. 400 grams of the partiallyhydrogenated cardanol were then sulfurized with 28 grams of sulfur at330-350* 1!, which was calculated to give a sulfur content in theproduct of from etc 7%. The resulting par ially hydrogenated sulfuriaedcardanol was then dissolved in toluene and 115 grams of pyridine wereadded.

To this solution was then added 80 grams of POCh at room temperature.The reaction mixture was allowed-to stand for 16 hours and wasthereafter stirred .at 85-75 C. for an additional four hours. Thephosphate ester was then flltered free of pyridine hydrochloride and;the '01- vent removed by stripping. The analysis of the trl-phoephateester of partially hydrogenated sulfurisedc'ardanol was as follows; 2 I

Found Theory,

' The efl'ectivenees of the phosphoric deters of the present inventionas extreme pressure agents when incorporated in lubricating oils hasbeen demonstrated by tests conducted on analmen testing machine. I'brthese the product obtainedbythefomoingexamplewaeincorpo rated in asolvent-refined. dewaxed. lfld-Conti'nentlubricating'oilofan8..d.l80grade.'1h'

genus of the Anacardiaceae family which have been modified by theaddition of substituent groups selected from the class consistingofsulfur and halogen in the unsaturated alkyl radicals thereof. I v v 3. Alubricant comprising a major proportion of a hydrocarboi'i oil and aminor proportion, suiilcient to impart,extreme pressure propertiestosaid hydrocarbon oil, of a substituted alkyi phenyl ester of phosphoricacid, said substituted alkyl phenyl ester-being derived from theunsaturated alkyl phenols present in or derived from the oils extractedfrom the Anacardium genus,

of the A'nacardiaceae family which have been modified by the addition ofsubstitutent groups in the unsaturated alkyl radicals thereof. saidsubstituent groups being selected from the consisting of sulfur and ahalogen.

4. A lubricant comprising a. hydrocarbon containing (Ll-10.0% by mm 0! asubstituted aikyl phenyl ester of.phoephoric acid, said sub- 'stituted'alkyi phenyl ester being derived mm the unsaturated alkyl phenolspresent in or derived fromcashew nutshell oil which have been I halogenin the unsaturated alkyl radicals thereof.

a. a lubricantoomprising a mineral lubricating oil containing 0.1-10.0%by weight of a submodiiled by'the additiomofeubstituent groupsselectedfrom'theclasecomisting ofsulfurand halogenintheunsaturatedalkylradicalstheretherein 0.1-10-0 weisht of a alkylphnrleeterofpboephoric stiuted alkyl.phenyluterbeing derltheuneaturatedelblphenohpseeentinin' Poundsrived from the oilsextracted-from the Anacardium genus of the Ana'cardiaceae family, andchar,- acteriaed by the addition of at least one substituent groupselected'from the class consisting of sulfur and halogen in theunsaturated alkyl radicals thereof. 7. A lubricant comprising a minerallubricatin oil containing (Ll-10.0% by weight of a substituted tri-alkylphenyl ester of phosphoric acid, said substituted tri-alkylphenvl esterbeing derived from the unsaturated alkyl phenols present in or derivedfrom oils extracted from the Anacardium genus of theAnacardiaceaeIfamiIy which have been modified by the additionofsubstituent groups selected from the class consisting of sulfur andhalogen in the unsaturated alkyl radicals thereof.

a. Alubricant comprising a mineral lubricat 13. A lubricant comprising ahydrocarbon oil and 0.l- 10.0% byweight of partially hydrogenatedsulfurized tri-cardanyl phosphate.

14. A high pressure lubricant comprising lubrieating oils and greaseshaving incorporated therein (Ll-10.0% byiweight of partiallyhydrogenated suli'urized tri-cardanyl phosphate.

15. A lubricant comprising a hydrocarbon 'oil containing a smallquantity, sumcient to impart saturated alkyl phenols present in orderived from cashew nut shell oil. and characterized by the addition ofat least one substituent group selected from the class consisting ofsulfur and halogen in the \msaturated alkyl radicals thereof.

10. A lubricant comprising a hydrocarbon oil containing (ll-10.0% byweight of a substituted alkyl phenyl esterof phosphoric acid saidsubstituted alkyl phenyl ester being derived from the partiallyhydrogenatedunsaturated alkyl p s present in or derived from cashew nutshell oil and characterised by the addition of ,at least one substituentr up selected from the class consistin: of sulfur and halogen in theunsaturated alkyl radicals thereof.

11. A lubricant comprising a hydrocarbon oil and 0.140.095 by weight ofsulfurised til-cardanyl phosphate.

12. A lubricant comprising a mineral lubricating oil and 0.140. byweight of sulfurized tricardanyl mm.

extreme pressure properties to said hydrocarbon oil, of a substitutedalkyl phenyl ester of phosphoric acid, said substituted alkyl phenylester being derived from the unsaturated alkyl phenols present in orderived from cashew nut shell oil which have been partially hydrogenatedand modified by the addition of sulfur to the remaining unsaturatedlinkages of the alkyl radical thereof.

16. A lubricant comprising a hydrocarbon oil containing a smallquantity. suillcient to impart extreme pressure properties to saidhydrocarbon oil. of a substituted alkyl phenyl ester of phos-v phoricacid, said substituted 'alkyl phenyl ester being derived from theunsaturated alkyl phenols present in or derived from cashew nut shelloil which have been partially hydrogenated and modified by the additionof chlorine to the remaining unsaturated linkages of the alkyl radicalthereof.

17. A lubricant comprising a hydrocarbon oil containing a smallquantity. suiiieient to impart extreme pressure properties to saidhydrocarbon oil, of said substituted alkyl phenyl ester of phosphoricacid, said substituted alkyl phenyl ester being derived from theunsaturated alkyl phenols present in or derived from cashew nut shelloil which have been modified by the addition of sulfur to theunsaturated linkages of the alkyl radical thereof. b b

18. A lubricant comprising a hydrocarbon oil containing a small quantitsuillcient to impart extreme pressure properti to said hydrocarbon oil.of a substituted alkyl phenyl ester of phosphoric acid, said substitutedalkyl phenyl ester being derived from the unsaturated alkyl phenolspresent inor derived from cashew nut shell oil which have been modifiedby the addition of chlorine to the unsaturated linkages of the alkylradical thereof.

LEBBEUB C. KEMP, Jr.

